Production of olefine ethers



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` UNITED e STATES INDUCTION F 0m Henry Charleaton,\V.Va.. V(lachenchemicals ofNewYork and Y Pei-kill.' allgnontoarbldeanl (lorporatimaeorporatian- PATENT ori-'Ical GranvllleA.

i No Drawllla'. Application January '1, 1936, Y serial Na 57.886

realm. (cian-151) Y nonvolatile amines as catalysts for promoting the reaction between the strong alkali and the betachiorinated ether. Throughout this specification and the appended claims the term "nonvolatile amine lwill be taken to include those amines which do not appreciably volatilize below about 150 C. This invention, however, is not limited to the use of amine catalysts of this class, and

more volatile amines may be used as catalysts as will more fully hereinafter appear.

A principal object of the invention is the provision of an improved process for making Aoleiine ethers in a simple ecient and economical mani ner. A feature o this invention involves the pro.- motion of the formation of unsaturated or oleiine ethers from beta-chlorinated ether-s by the action oi a strong alkali through the agency of a strongly basic amine. Another feature involves the use of the initial reactants primarily in the liquid phase. I

Y The amines which are suitable as catalysts for promoting this reaction may be'chcsen from the class of heterocyclic, alicyclic, aromatic, or aliphatic amines, and primary, secondary and tertiary amines or uimures thereof may be used. Ln general it is unnecessary to use large amounts of the amine catalyst, and from about to about 20% by weight, based on the amount of the Example I A mixture of about 2B parts by weight of solid sodium hydroxide in finely divided form and about o parts by weight of bis-beta. chloroethyl ether was agitated in an iron kettle for about 3 to 3%/2 hours at the boiling point ci' the mixture. To this boiling mixture was added about 4.5 parts by weight of triethanolamine andV the reaction was continued. The triethanole added as a catalyst to promote the reaction consisted of a mixture which contained, in addition yto the tertiary amine, small quantities of monoethanolamine Vand diethanolamine. After the addition of the amine catalyst and during the course of the reaction, the boiling point of the 5 mixture decreased to about 150 C. Y

The reaction products were recovered in the form o1' a distillate which included chloroethyl vinyl ether, divinyl ether and imchanged bis-beta chloroethyl ether, together with small amounts lilV of water. This distillate was removed continuously during the reaction through a ractionating column, the still head temperature of which was maintained at about 96 C. Tiieyield ofk chloro-V ethyl vinyl ether obtained was about 70% of the 15 f theoretical, based on the 'amount of sodium hydroxide employed.

In the reaction described, the bis-beta chloroethyl ether was present in considerable" excess over the theoretical amount required to react with the sodium hydroxide, and this factor maintained a liquid condition in the reaction kettie at all times. Ee solid alkali and the sodium chloride formed in the reaction were maintained in a finely divided state dispersed throughout the liquid in this reaction.

After the reaction was completed, water was added in substantial quantity to dissolve the salt,

'and fortifierl quantitiesA oi unreacted bis-beta chloroethyi ether were readily senarated from the 3@ salt solution by decantation.

Example il' Divinyl ether may be conveniently made from the chloroethyl vinyl ether obtained as described in Example' I, and it is preferably obtained from a mixture of this ether with bis-beta chloroethyl ether. i mixture of about Sii parts byweight each oi the two others (which may be replaced, if desired, by about lil parts by weight of bis- 4,9 beta ehloroethyl ether alone), was stirred with about 2G parts by weight oi laked sodium hydroxide for about 3 hours at the boiling point of the mixture. To this boiling mixture was added about 5 parts by weight of triethanoiaminaand 45 the reaction was continued with agitation.

The reaction products were removed, as in the previous example, as a distillate which in eluded chloroethyl vinyl ether, small amounts of water, and divinyl ether equivalent to a yield of about 70% ofthe theoretical. The still head of the fractionating column through which this distillate was removed, was maintained at from about-50 to about 76 C. The quantity of chloroethyl vinyl ether removed in the operation of this process was approximately equal to the quantity originally introduced in the starting mixture. This canl be reused, making the process substantially cyclical, or it may be puried and employed as such. If more pure divinyl ether is desired, this process may be varied by removing water through a decanter from about the middle of a fractionating column. This variation permits a lower still head temperature to be maintained, and the distillate will contain a more puredivinyl ether.

The processo! this -invention may be operated similarly to produce other ol'ene ethers. For example, chloroisopropyl isopropenyl ether and diisopropenyl ether can be easily prepared from liquid bis-beta dichloroisopropyl ether. By the process described in the examples above, it is likewise easy to produce vinyl isopropenyl ether from beta chloroethyl beta chloroisopropyl ether. Mixed ethers, such as vinyl ethyl ether' and vinyl butyl ether, can be readily obtained from beta chloroethyl ethyl ether and beta chloroethyl butyl ether, respectively.

Of the strongly basic, relatively nonvolatile amines which are particularly emcacious in promoting the reaction described above, the hydroxyalkyl amines were found to be the most eiective. Of these, the ethanolamines produced very eilicient and highly desirable results. Triethanolamine was found to be particularly effective, and is preferred as a catalyst. Diethanolamine and monoethanolamine can also be used, and both are effective whether used in the pure state or in admixture with each other or with triethanolamine. piperidine, diamylamine, pyridine, aniline and dimethyl aniline. i

The presence of all the reactants. except the alkali, in the liquid phase appears to be of critical importance. By the operation of this process, relatively low temperatures are suiilcient, and the yields obtained are in every case good. The ease of operation and the effectiveness of this process will make its value apparent.

The process described above is susceptible o1' Examples of other active catalysts arev modincation and such modifications are included within the invention as defined by the appended claims. A

We claim:

1. Process for the production of olonne ethers which comprises treating a beta-chlorinated aliphatic ether with a strong alkali in the presence of a catalyst essentially composed of a strongly lligsic amine which isnot volatile below about 2. Process ior the production of olellne ethers which comprises treating a beta-chlorinated aliphatic ether with a strong alkali in the presence of a catalyst-essentially composed of a hydroxyalkylamlne. v

3. Process for the production of olene ethers which comprises treating a beta-chlorinated aliphatic ether with a strong alkali in the presence of an ethanolamine. 4. Process for the production of oletine ethers which comprises treating a beta-chlorinated aliphatic ether with a strong alkali in the presence of from about 5% to about,20% of a catalyst selected, from the group consisting of trlethanolamine, diethanolamine, monoethanolamine, and mixtures thereof.

5. Process for the production of oleilne ethers which comprises treating a beta-chlorinated aliphatic ether in the liquid phase witha strong alkali in the presence of a catalyst essentially composed of a strongly vbasic amine such as a hydroxyalkylamine.

6. Process for the production of oleiine ethers which comprises treating a beta-chlorinated aliphatic ether in the liquid phase with a finely divided strong alkali in the'presenceof a catalyst essentially lcomposed of a strongly basic amine such as a hydroxyalkylamine.

7. Process for making vinyl ethers which comprises heating bis-beta chloroethyl ether in the liquid phase with sodium hydroxide in the presence of from about 5% ethanolamine,

HENRY C. CHITWOOD.

GRANVHLE A. PERKINS.

to about 20% of an- 

